TWI401297B - Photo-curable compositions - Google Patents

Description

Photocurable composition

The present invention relates to a curable composition, in particular, rapid polymerization by irradiation of an active energy ray such as ultraviolet rays or visible light, and a photocurable composition for use as an elastic sealant for various members.

As a method of joining and sealing an electric wire, an electromechanical component, an automobile component, an optical component, and various mechanical parts, a method in which a molded gasket made of rubber is pressed against a sealing surface or a sealing surface is used. A method of sealing by a liquid sealant. The method of using the gasket, the problem of high material loss due to the loss of the material of the punching sheet or the molding process of the gasket, or the occurrence of the trap when the gasket is used for a long time, the tightening torque of the screw is reduced or the leakage occurs from the contact surface. . In addition, a room-temperature hardening type polyoxyalkylene material (polyoxyalkylene RTV) or a urethane (meth) acrylate which is hardened by reaction of moisture in the atmosphere with a bath surface is used as an anaerobic liquid containing a main component of a urethane (meth) acrylate. The sealant is applied by an automatic coater and then combined as it is. However, the curing time of the sealant after the combination is not sufficient, and the uncured liquefied sealant flows due to the internal pressure and leaks, and the initial pressure resistance is low. In order to solve the above problems, in recent years, proposals have been made for various methods of rapidly curing the light to form a sealant composition.

There are many types of such photocurable resin compositions known.

An example of the photocurable composition comprising a polyfunctional (meth) acrylate, a bifunctional (meth) acrylate having a crosslinked ring structure, and a photopolymerization initiator (Japanese Patent No. 2953598) Light and moisture-curable composition of a poly(meth)acrylic acid group having a (meth)acrylic group and a hydrolyzable group, a photopolymerization initiator, and a moisture curing catalyst in the molecule (JP-A-2000-178535) Thermosetting composition of resin, rubbery polymer microparticles, inorganic filler, thermal latent oxygen hardener, and high-softening point polymer microparticles (JP-A-2000-347203) A photocurable sealant composition containing an acrylate (meth) acrylate monomer, a photopolymerization initiator, and a filler as a main component (JP-A-2001-163931).

Sealants Generally, hardeners are expected to maintain their full flexibility, solvent resistance or moisture permeability isolation, and also under the harsh conditions of overheating.

[Object of the invention]

It is an object of the present invention to provide a hardenable composition of a sealant which exhibits excellent properties.

Another object of the present invention is to provide a cured product, particularly solvent resistance, moisture permeability, flexibility, and impact resistance, particularly for liquid crystal display elements, organic EL elements, dye-sensitized solar cells, electronic paper, and lithium ions. A photocurable resin composition of a sealing agent such as a battery, a polyacene battery, an OXYRIDE (OXY nickel hydoRIDE) battery, a capacitor, or a fuel cell.

Another object of the present invention is to provide a photocurable resin composition in which a cured product has a sealing function under high temperature conditions, and is particularly useful as a sealant for an easily high heat member such as an automobile engine portion.

[Abstract of the Invention]

According to a first aspect of the present invention, a photocurable composition characterized by (A) a hydrogenated polybutadiene having a (meth) acrylonitrile group, (B) a saturated aliphatic hydrocarbon elastomer, and (C) a photopolymerization initiator Things.

In the second aspect of the present invention, the component (A) is a general formula: (R ¹ and R ² are each independently a hydrogen atom or a methyl group, and R ³ and R ⁴ are each independently a linking group, an oxygen atom or a divalent organic group having 1 to 16 carbon atoms, and x:y=0 to 100: 100~0, n is 15~150).

The first photocurable composition shown above.

In the third aspect of the present invention, the first and second photocurable compositions of (D) a chain aliphatic or alicyclic monofunctional (meth) acrylate having 5 or more carbon atoms are further contained.

In the fourth aspect of the invention, the component (B) is 20 to 80 parts by weight, the component (C) is 0.5 to 5 parts by weight, and the component (D) is 0 to 80 parts by weight or less. The first to third photocurable compositions.

In the fifth aspect of the invention, the component (B) is at least one of the first to fourth photocurable compositions selected from the group consisting of hydrogenated polybutadiene and polyisobutylene.

In the sixth aspect of the invention, the component (B) is a first to fifth photocurable composition having a molecular weight of 5,000 or less.

In the seventh aspect of the invention, the component (B) is a polyisobutylene having a molecular weight of 500 to 50,000, and the first and second photocurable compositions of the component (A) in an amount of 20 to 60 parts by weight based on 100 parts by weight of the component (B). Things.

In the eighth aspect of the invention, the cured product of the photocurable composition is a photocurable composition of the seventh modification having a compression set at 150 ° C of 20% or less in accordance with JIS K6262.

In the ninth aspect of the invention, the component (B) is of the general formula: Polyisobutylene (R1, R2 is an alkyl group or an alkenyl group, and m is 8 to 800).

In the tenth and (B) component of the present invention, the seventh to ninth photocurable compositions having a molecular weight of 2,000 to 50,000 are used.

According to a twelfth aspect of the present invention, a photocurable composition according to any one of claims 1 to 10 is applied to a solid substrate to be subjected to sealing bonding, and a sealing method characterized by curing the composition by light irradiation.

[embodiment of the invention]

The component (A) of the curable composition of the present invention is a hydrogenated polybutadiene having a (meth)acryl fluorenyl group. Here, the term "(meth)acrylonitrile" means an acryloyl group and/or a methacryloyl group.

The molecular structure of the component (A) has a hydrogenated polybutadiene backbone as the backbone, and has a (methyl) acrylonitrile group at the end, a hydrogenated polybutadiene molecule and a (meth) acrylonitrile group directly or suitably. The combination of the two-valent binding groups. A typical example thereof is as shown in the above general formula (1). The hydrogenated butadiene unit of the repeating unit of the hydrogenated polybutadiene constituting the main backbone is a hydrogenated 1,2-butadiene unit alone, hydrogenated 1,4-butadiene unit alone or both (ie x:y=0~100:100~0), hydrogenated 1,2-butadiene unit (x): hydrogenated 1,4-butadiene unit (y)=10~100:90~0 is ideal In particular, it is ideal to use 20~95:80~5 in combination. (A) component, usually by polymerization of butadiene by sodium anion polymerization or by cationic polymerization of Fricdel Craft, to produce liquid polybutadiene, in transition A liquid substance produced by adding a (meth) acrylonitrile group at the end after hydrogenation in the presence of a hydrogenation catalyst such as a metal can be appropriately selected from commercially available products.

The saturated aliphatic hydrocarbon elastomer of the component (B) is an elastomer of a saturated aliphatic hydrocarbon, and the molecular terminal may be an unsaturated group such as an aryl group according to a production method or the like. The component (B) has excellent compatibility with the component (A) and is preferably rubber-elastic at normal temperature, and is particularly preferably hydrogenated polybutadiene or polyisobutylene.

The photopolymerization initiator of the component (C) is generally known to be suitable for use as a photoradical polymerization initiator. These photopolymerization initiators are classified into an intramolecular split type (P1 type) and a hydrogen induced type (P2 type) due to a difference in chemical structure (molecular binding energy). Specific examples of P1 include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, and diethoxybenzene. Ethyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)one, Acetophenones such as 1-hydroxycyclohexyl phenyl ketone, benzophenones such as benzophenone, acetoin, acetophenone, and benzyl dimethyl ketal; Acyl phosphine oxide), titanium oxide (titanocene) compound, and the like. Further, specific examples of the P2 type include benzophenone, benzoquinonecarboxylic acid, methyl benzoquinone, 4-phenylbenzophenone, hydroxybenzophenone, and 4-benzoquinone-4'. -Methyldiphenyl sulfide, benzophenones such as 3,3'-methyl-4-methoxybenzophenone, anthranyl ketone, 2-chlorodecyloxy ketone, 2-methyl An anthranoxy ketone such as a quinone ketone, a 2,4-dimethyl methoxy ketone or an isopropyl methoxy ketone. The photo-radical polymerization initiator may be used singly or in combination of two or more kinds, and may be used in combination with the P1 type, the P2 type, or the P1 type and the P2 type.

The amount of the photopolymerization initiator to be used may be an amount sufficient for photopolymerization, and the resin component in the composition is preferably 0.1 to 10 parts by weight per 100 parts by weight, particularly preferably 0.5 to 5 parts by weight.

The component (D) is a chain aliphatic or alicyclic monofunctional (meth) acrylate monomer having 5 or more carbon atoms, and the linear carbon number of the aliphatic chain portion is preferably 5 to 20, 8~ 16 is more ideal. The monofunctional (meth) acrylate used in the present invention is not suitable for holding a polar structure such as a hydroxyl group or an amine group. Therefore, the chain aliphatic and alicyclic portions of the ester moiety are preferably formed from hydrocarbons. The chain fat monofunctional (meth) acrylate monomer, specifically, for example, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, laurel Base (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, hexadecyl (meth) acrylate, etc. . Specific examples of the alicyclic (meth) acrylate component include cyclohexyl (meth) acrylate, raw spine alkyl (meth) acrylate, dicyclopentyl (meth) acrylate, and bicyclo ring. Pentenyl (meth) acrylate, isofulrone keto (meth) acrylate, and the like.

The photocurable composition of the present invention may be blended with other additives in an appropriate amount without impairing the characteristics of the resin composition of the present invention. Other additives such as a coloring agent such as a sensitizer, a pigment, and a dye, a polymerization stopper, a pigment, an antifoaming agent, a coupling agent, an organic or inorganic filler, and the like can be exemplified.

The sealant of the photocurable composition of the present invention is applied to a bonded substrate, and is cured by light irradiation in a usual manner, and can be suitably used in various fields of the sealant, and an ideal component or amount is selected in accordance with the requirements of the properties of the sealant.

In the first type, the cured product is excellent in solvent resistance, moisture permeability, flexibility, and impact resistance, and is particularly useful as a liquid crystal display element, an organic EL element, a dye-sensitized solar cell, an electronic paper, or a lithium ion battery. A photocurable resin composition of a sealant such as a polyacene battery, an OXYRIDE (hydroxy nickel hydroxide) battery, a capacitor, or a fuel cell.

In this case, for 100 parts by weight of the component (A), the component (B) is 20 to 80 parts by weight, the component (C) is a catalyst amount, particularly 0.5 to 5 parts by weight, and the component (D) is 0 to 80. The component is preferably 20 to 60 parts by weight, and the component (A) is preferably a low molecular weight compound having a molecular weight of 500 to 5,000.

In the photocurable composition of the first type, the cured product is provided with a solvent-resistant, moisture-permeable barrier property, flexibility, and impact resistance, and can be absorbed when used as a sealant for a paste-sensing solar cell or the like. The expansion and contraction of the adhesive material with the thermal cycle is alleviated by the stress at the interface, and when the component (D) is used, the surface adhesiveness is reduced at the time of hardening, and it is also suitable for the opening of the surface of the CIPG or the sealant. Location.

In the second type, the cured product also has a sealing function under high temperature conditions, and particularly has a photocurable resin composition for a sealant which is easily a high heat member such as an automobile engine portion.

In this case, the composition is composed of (A) to (C) components, and the component (B) has a molecular weight of 500 to 50,000, preferably 2,000 to 50,000, and 100 parts by weight of the component (B). The component is 20 to 60 parts by weight, and the component (C) is a catalyst amount, and particularly preferably 0.5 to 5 parts by weight.

Typical examples of the polyisobutylene are, for example, the above general formula (2), and can be appropriately selected from commercially available products.

The composition of the second type can provide an elastic sealant having a compression set of 20% or less at 150 ° C in accordance with JIS K6262, and is particularly effective for sealing a member requiring heat resistance such as an automobile engine.

The invention is specifically described by way of examples, but the invention is not limited to the examples.

Example of the first type

The materials used are as follows. "TEAI 1000" (manufactured by Nippon Soda Co., Ltd.) having hydrogenated polybutadiene (A) having a (meth) acrylonitrile group at the end, "SPBDA" (manufactured by Nippon Organic Co., Ltd.), and "TEA 1000" of component (A) (Polymerized polybutadiene with (meth)acryloyl group at the end, "UE 8200" (epoxy acrylate manufactured by Dainippon Ink Co., Ltd.), "UF 8001" (Japan) Hydrogenated polybutadiene ("BI 2000": manufactured by Nippon Soda Co., Ltd.) and polyisobutylene ("G 1000" and "G 3000" manufactured by Rong Chemical Co., Ltd.), saturated aliphatic elastomer (B) :Compared unhydrogenated polybutadiene ("BI 2000": manufactured by Nippon Soda Co., Ltd.), polyisobutylene (LIR-30): manufactured by KURARE Co., Ltd., manufactured by BASF Japan Co., Ltd., "Photopolymerization initiator" Iruka Cure 184" (#184, manufactured by Ciba Speciality Chemicals Co., Ltd.), a chain aliphatic and a cycloaliphatic monofunctional (meth) acrylate component (C) having a carbon number of 5 or more, and an isofluranone acrylate (D) component ( IBXA), isodecyl acrylate (INA), lauryl acrylate (LA), component (D) compared to n-butyl acrylate (n-BA) 2-hydroxyethyl acrylate (HEMA), N, N'- alkyl acrylate (DMMA).

These materials were blended in accordance with Tables 1 to 3 (the amounts described in the tables are parts by weight), and the mixture was stirred at 50 ° C for 1 hour using a mixer to obtain each composition. Each of the obtained compositions was evaluated by various test methods shown below, and the results are collectively shown in Tables 1 to 3.

[Compatibility test] Confirmation of compatibility The 20 g of each composition was placed in a 50 mL glass bottle on the basis of the examples and the comparative examples, and the mixture was allowed to stand at 25 ° C for 24 hours, and the separation state was visually confirmed, and it was judged that no separation was ○, and separation was observed. For ×.

[Hardness Test] Hardness 2 g of each composition was placed in a 25 Φ plastic lid on the basis of the examples and the comparative examples, and irradiated with ultraviolet rays at 3000 mJ/cm ² to measure the average value of any five points by a durometer (Duro Meter type A). The target value is 50.

[Solvent resistance test] 2 g of each composition of the examples and comparisons was placed in a 25 Φ plastic cover, and irradiated with ultraviolet light at 3000 mJ/cm ² , and the cured product was first immersed in acetonitrile by a weight (condition: 60 ° C × 96 hours). Thereafter, the hardened material was taken out, the surface was lightly wiped, and the weight was measured to determine the weight change rate before and after the immersion. The target value is ±15% or less by weight.

[Moisture permeability test] The measurement was carried out in accordance with JIS Z 0208 (measurement conditions: 60 ° C × 95% RH). The measurement film was prepared by coating a resin on a polyfluorinated ethyl acetate plate (having a film thickness of about 100 μm), and cutting the specified container shape by irradiating a cured product of ultraviolet rays of 3000 mJ/cm ^{2 to} chlorinate about 1 g in the container. Calcium health. The weight was determined as a reference value after 24 hours, and the end point was obtained when the change in weight over time was saturated. The target value is 80 g/cm ² . 24h.

When the unhydrogenated polybutadiene having a (meth) acrylonitrile group at both ends shown in Tables 1 and 2 is compared with the case where the main chain is hydrogenated polybutadiene, neither of them can be obtained. Full results. On the one hand, the compatibility of the polymer backbone with the urethane or epoxy acrylate is inferior to the component (B). When the saturated aliphatic elastomer is small, the solvent resistance is lowered, and when it is too large, the moisture permeability is lowered. Further, when the main chain of the saturated fatty elastomer is polyisobutylene composed of a repeating unit having 5 carbon atoms, the compatibility is deteriorated.

As shown in Table 3, when the chain aliphatic or alicyclic functional (meth) acrylate having a carbon number of 5 or more is added in an amount of 80 parts by weight or more based on the component (A), the solvent resistance and the moisture permeability are excellent. Get softness. Further, when a (meth) acrylate component having a carbon number of less than 5 is added, the compatibility of the resin is poor, and the moisture permeability is also lowered.

Example of the second type:

The materials used are as follows. EP 600 A (terminal allylated polyisobutylene (molecular weight 20,000) manufactured by Kaneka Chemical Industry Co., Ltd.), EP 400 A (terminal allylated polyisobutylene (molecular weight 10,000) manufactured by Kaneka Chemical Industry Co., Ltd.), EP 200 A (terminal allylated polyisobutylene (molecular weight 5,000) manufactured by Kaneka Chemical Industry Co., Ltd.), G 3000 (polyisobutylene (part 2,200) manufactured by BASF Corporation), EP100 S (terminal alkoxylate manufactured by Kaneka Chemical Industry Co., Ltd., Japan) Allylated polyisobutylene, SPBDA (terminal propylene hydrogenated polybutadiene (molecular weight 6,000) manufactured by Otsuka Organic Co., Ltd.), L-1253 (endone methacrylic acid hydrogenated polybutadiene manufactured by Creatone Polymer Japan) ), BAC-45 (terminal propylene-deuterated unhydrogenated polybutadiene manufactured by Otsuka Organic Co., Ltd.), UC-102 (terminal propylene-deuterated hydrogenated polyisobutylene manufactured by Claray Co., Ltd.), L-207 (endone ring manufactured by Creatone Polymer Japan) Oxidative hydrogenated polybutadiene), Darocure 1173 (photo-radical polymerization initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one) manufactured by Ciba Geigy, Japan), Rhodoresil 2074 (Rhodia Corporation) Photo-cationic cationic polymerization initiator ((tricumyl)iodotetrakis(pentafluorophenyl)boron Acid ester)).

These materials were mixed and stirred as shown in Table 4 to separately debug the materials. Each of the obtained samples was subjected to an evaluation test shown in the following item, and the results are shown in Table 5.

[Compatibility test] Confirmation of compatibility The 20 g of each composition was placed in a 50 mL glass bottle on the basis of the examples and the comparative examples, and allowed to stand at 25 ° C for 24 hours, and the separation state was visually confirmed.

[Photohardening Test] Hardness 3 g of each composition was placed in a 25 Φ plastic lid on the basis of the examples and the comparative examples, and irradiated with ultraviolet rays at 3000 mJ/cm ² to visually observe the hardened state.

[Hardness Test] The hardness of the resin was measured by using two sheets of the cured product in the photocurability confirmation test, and the average value of any five points was measured by a durometer (Duro Meter type A or C).

[State of the cured product after the compression set test, compression set test] The compression set test was carried out in accordance with the following operation (JIS K6262 test). It is about to harden into a disc-shaped composition with a diameter of 29.0±0.5 mm and a thickness of 12.5±0.3 mm. It is placed between the stainless steel plates with smooth surface processing and is compressed by screws and screws to a soft steel partition with a thickness of 9.38±0.01 mm. The thickness of the board. After the test piece was placed in a 150 ° C thermostat bath for 72 hours, it was quickly taken out by a compression device and left at about 23 ± 5 ° C for about 30 minutes. After the specified time, the appearance of the cured product was observed and the thickness was measured. The compression set is also calculated by the following formula.

Cs={(t ₀ -t ₁ )/(t ₀ -t ₂ )}×100

From the above, it is understood that when 100 parts by weight of a relatively high molecular weight polyisobutylene is blended with 20 to 60 parts by weight of a hydrogenated polybutadiene having a (meth) acrylonitrile group, it is known that the compatibility is good and the photocurability is also good. The compression set test results were also good.

Claims (6)

A photocurable composition characterized by (A) a hydrogenated polybutadiene having a (meth) acrylonitrile group, (B) selected from hydrogenated polybutadiene, and represented by the following general formula (2) a saturated aliphatic hydrocarbon elastomer of polyisobutylene and (C) a photopolymerization initiator, (R1, R2 are an alkyl group or an alkenyl group, and m is 8 to 800). The photocurable composition according to claim 1, wherein the (D) aliphatic chain moiety or the alicyclic moiety has a chain aliphatic or alicyclic monofunctional (meth) acrylate having a carbon number of 5 or more. The photocurable composition according to claim 1 or 2, wherein the component (B) is a polyisobutylene having a molecular weight of 500 to 50,000, and the component (A) is 20 to 60 parts by weight based on 100 parts by weight of the component (B). . For example, the photocurable composition of claim 1 or 2, wherein the component (A) is of the general formula: (R ¹ and R ² are each independently a hydrogen atom or a methyl group, and R ³ and R ⁴ are each independently a divalent linking group, an oxygen atom or a divalent organic group having 1 to 16 carbon atoms, x:y=0~ 100:100~0, n is a compound represented by 15 to 150), and the component (B) is 20 to 80 parts by weight, and the component (C) is 0.5 to 5 parts by weight, based on 100 parts by weight of the component (A). The component (D) is 0 to 80 parts by weight. The photocurable composition according to claim 1 or 2, wherein the component (B) represented by the general formula (2) is a polyisobutylene selected from the group consisting of R1 and R2, or R1 and R2. Any one or more of polyisobutylenes which are alkenyl groups and have a number average molecular weight of from 5,000 to 20,000. A sealing method characterized in that a photocurable composition according to any one of claims 1 to 5 is applied to a solid substrate to be bonded and bonded, and the composition is cured by light irradiation.